Contact

Porträt Prof. Dr. Kvashnina, Kristina; FWOS

Prof. Dr. Kristina Kvashnina

Head of the Synchrotron Science Department
Responsible for the BM20 (ROBL) beamline at ESRF
k.kvashnina@hzdr.de
Phone: +33 476 88 2367

Department of Synchrotron Science

Molecular Structures

Research

The Department of Molecular Structures conducts synchrotron-based research, offering a robust toolkit for scientists investigating materials containing actinides and lanthanides.

Experiments take place at the Rossendorf Beamline of The European Synchrotron (ESRF), in Grenoble (France) which is specifically dedicated to the actinide science and research on radioactive waste disposal. The beamline consists of four experimental stations -XAFS, XES, XRD-1, XRD-2:

  • XAFS station with fluorescence and transmission detection for X-ray Absorption Fine-Structure (XAFS) spectroscopy, including (conventional) X-ray Absorption Near-Edge Structure (XANES) and Extended X-ray absorption fine-structure (EXAFS) spectroscopies
  • XES with a 5-crystal Johann-type spectrometer for high-energy-resolution fluorescence-detection X-ray absorption near-edge spectroscopy (HERFD-XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) measurements.
  • XRD-1 station with a heavy-duty, Eulerian cradle, 6-circle goniometer for (high-resolution) powder X-ray diffraction (PXRD), surface-sensitive crystal truncation rod (CTR) and resonant anomalous X-ray reflectivity (RAXR) measurements
  • XRD-2 station with a Pilatus3 x2M detector stage for single crystal X-ray diffraction (SCXRD) and in situ/in-operando PXRD measurements.

Our research provides detailed insights into the structural and electronic properties of actinide and lanthanide-containing materials across various scientific disciplines, including physics, chemistry, environmental science, and geoscience. We study fundamental electron interactions, bonding properties, probing the local structures and oxidation states of complex systems. Data analysis is performed with the help of electronic structure calculations. 

EXAFS, HERFD-XANES, XES and RIXS is not restricted to crystalline solids, but can be applied to a wide range of samples, to derive information on e.g. aqueous speciation, complexation with dissolved inorganic ligands like chloride, sulfate or nitrate, complexation with organic ligands like acetate or humic acid, interaction with bacteria and plants, sorption to mineral and rock surfaces for actinides an other metals and metalloids. Due to the high penetration depth of the employed hard X-rays, the methods are suited to study chemical reactions in-situ/in-operando, for instance at very low or high temperatures, under special atmospheres, or under electrochemical potentials.

More about Rossendorf Beamline

Latest publication

Core-Excited States of Linear and Bent Uranyl Complexes: Insights from High-Energy Resolution X‑ray Spectroscopy and Relativistic Quantum Chemistry

Aldair Misael, W.; Amidani, L.; März, J.; Bazarkina, E. F.; Kvashnina, K.; Vallet, V.; Severo Pereira Gomes, A.

Abstract

Advanced X-ray spectroscopic techniques are widely recognized as state-of-the-art tools for probing the electronic structure, bonding, and chemical environments of the heaviest elements in the periodic table. In this study, we employ X-ray absorption near-edge structure measurements in high-energy resolution fluorescence detection (HERFD-XANES) mode to investigate the core states arising from excitations out of the U 3d3/2 (M4 edge) levels for molecular complexes in which the uranyl moiety deviates from linearity to varying degrees, and in particular systems containing the UO2Cl2 group such as UO2Cl2·n(H2O) and UO2Cl2(phen)2, which in the latter case exhibits a pronounced O−U−O bending angle. These U M4-edge HERFD-XANES spectra are compared with those of other uranyl complexes reported in the literature. This evaluation is complemented by ab initio relativistic quantum chemistry simulations on the [UO2(NO3)2·n(H2O)], UO2Cl2·n(H2O), and UO2Cl2(phen)2 systems, using two-component time-dependent density functional theory (TD-DFT) with the CAM-B3LYP functional, employing the Tamm-Dancoff approximation (2c-TDA). Our 2c-TDA simulations show modest deviations from the HERFD-XANES data, with peak splittings differing by less than 1 eV from experimental values. These core-excited states were further characterized by natural transition orbital (NTO) analysis. Overall, our results highlight the influence of equatorial ligands on the spectroscopic signatures, particularly pronounced in UO2Cl2(phen)2, where the U 3d3/2 → 5fσd u* satellite transition appears at lower energies compared to the other systems studied

Keywords: uranyl; HERFD XANES

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Permalink: https://www.hzdr.de/publications/Publ-42122

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Team

Head

NameBld./Office+49 351 260Email
Prof. Dr. Kristina KvashninaROBL/21.6.04+33 476 88 2367
k.kvashnina@hzdr.de

Employees

NameBld./Office+49 351 260Email
Dr. Lucia AmidaniROBL/14.1.04+33 476 88 1982
Dr. Nils BaumannROBL/21.6.03+33 476 88 2849
Clara Lisa E SilvaROBL/14.1.04+33 476 88 2044
Jörg ExnerROBL/BM20+33 476 88 2372
Dr. Christoph HennigROBL/21.6.02a+33 476 88 2005
Dr. Eleanor Sophia Lawrence Bright+33 476 88 2462
Dr. Damien PrieurROBL/21.6.03+33 476 88 2463
Dr. André Roßberg801/P3162758
Anne Thielena.thielenAthzdr.de
Dr. Sami Juhani Vasalas.vasalaAthzdr.de